Patent GB-816749-A (GB)
Title: New oxdiazole disazo dyestuffs and process for their manufacture
IPC: C09B43/00
Filed: 1955-07-06
Abstract: Oxdiazoles of formula <FORM:0816749/IV (a)/1> where n is 1 or 2 and R and R1 are organic residues in which R1 contains an azo link and is bound to the oxdiazole ring by a carbon atom of an aromatic nucleus may be used for colouring polyvinyl chloride.  Preferably the oxdiazoles are free of water-solubilizing groups.  In examples, which describe the colouring of polyvinyl chloride in red, blue and yellow shades, R1 is derived from 2-methyl-4- and -5-chloro-, 2,5-dimethoxy-4-chloro- and -benzoylamino-, 2-methyl- and -carbethoxy-1-aminobenzenes --> b -naphthol, m- and p-aminobenzoic acids and 4-chloro- and -methoxy-3-aminobenzoic acids --> 4 - chloro - 2,5 - dimethoxy - 1 - acetoacetylaminobenzene, 5 - nitro - 4 - aminobenzoic acid --> 2-chloro-acetoacetylaminobenzene, 2 - carbutoxy - 1 - aminobenzene --> 4 - methoxy - 3 - acetoacetyl - aminobenzoic acid, 4 - methyl - 2 - nitro - 1 - aminobenzene --> 1 - phenyl - 3 - methyl - 5 - pyrazolone and 2 - nitraniline --> 1 - (21 - chlorophenyl) - 3 - methyl - 5 - pyrazolone and R is -CH=CH- or phenyl.  For the preparation of the dyestuffs see Group IV (c). Specification 730,384 is referred to.ALSO:The invention comprises dyestuffs of formula <FORM:0816749/IV (c)/1> where n is 1 or 2, R and R1 are organic residues and R1 contains an azo link and is bound to the oxdiazole ring by a carbon atom of an aromatic nucleus.  They are made by treating a compound of formula <FORM:0816749/IV (c)/2> where n is 1 or 2 and R and R1 are acyl residues derived from carboxylic acids and bound to -NH-NH- by the -CO- groups and in which the CO groups of the residues R1 are bound to aryl carbon atoms of residues containing azo links, with thionyl chloride.  The above compounds, where n is 1, are made by acylating hydrazine with appropriate acylating agents which may contain the required azo groups or the acylated hydrazine may be coupled with a diazo compound.  Hydrazine and acylating agents derived from mono- and dicarboxylic acids may be condensed in either order of succession in the mol. ratio of 2, 2, 1 to provide products where n is 2 and azo groups introduced into the products if necessary.  Acylating agents mentioned are those obtained by coupling a diazotized aniline carboxylic acid with a component free from carboxylic or sulphonic acid groups, e.g. acylacetic acid esters or amides, pyrazolones, phenols, dioxyquinolines, a - or b -naphthols and 5,8-dichloro-1-naphthol, preferred being compounds containing a fused ring system as in 2-oxy-diphenylene oxide-3-carboxylic acid, 2-oxy-carbazole- and -anthracene-3-carboxylic acids and especially 2-naphthol-3-carboxylic acid.  Preferably diazo compounds used should be capable of providing i.e. colours, e.g. those of the benzene series, which may contain substituents such as chlorine, alkyl, alkoxy, nitro or acylamino groups.  Oxalic, fumaric and iso- and tere-phthalic acids are specified dicarboxylic acids. Acylation is effected in known manner. Preferred acylating agents containing azo groups are carboxylic acid halides which may be obtained as in Specification 730,384. Advantageously the diacyl hydrazines do not contain water-solubilizing groups.  Ring closure with thionyl chloride is preferably effected by heating in an inert organic solvent such as chloro- or nitro-benzene.  The products may be used as pigments (when water-solubilizing groups are absent) and as such are used in pigment printing processes, for colouring spinning masses of viscose, cellulose ethers or esters or superpoly-amides or urethanes, lacquers, synthetic resins, e.g. aminoplasts, phenoplasts, polyvinyl chloride, polystyrene, polyethylene, polyvinyl, rubber casein, silicones, solutions of acetyl- and nitro-cellulose, cosmetic preparations and laminated plates.  In Examples, in which ring closure is effected with thionyl chloride: (1) the dyestuff 1-amino-2-methyl - 4 - chlorobenzene --> 2 - naphthol -3-carboxyli acid is treated with thionyl chloride and the acid chloride thus obtained reacted with hydrazine hydrochloride to yield a diacyl hydrazine which is ring closed; in (2) 1-amino-2-methyl-5-chlorobenzene and hydrazine sulphate are used instead of the 4-chloro-isomer and hydrochloride of (1); in (3) the monohydrazide of 2-naphthol-3-carboxylic acid is coupled with diazotized 4-chloro-2,5-dimethoxyaniline and the product treated with the acid chloride obtained by reacting the dyestuff 4-chloro-2,5-dimethoxyaniline --> 2-naphthol-3-carboxylic acid with thionyl chloride and the product ring closed; in (4) the acid chloride made from aniline-2-carboxylic acid ethyl ester --> 2-naphthol-3-carboxylic acid and thionyl chloride is treated with hydrazine sulphate and the product ring closed; in (5) the dyestuff 2-methyl-4-chloroaniline --> 2-naphthol-3-carboxylic acid hydrazide is treated with fumaric acid chloride and the product ring closed; in (6) the dyestuffs 2-methyl- or 4-benzoylamino-2,5-dimethoxy-aniline --> 2-naphthol-3-carboxylic acid hydrazide are treated with terephthalic acid and the product ring closed; in (7) the acid chlorides made from m- or p-aminobenzoic acid or 4-chloro- or -methoxy-3-aminobenzoic acid --> 4-chloro-2,5-dimethoxy-1-acetoacetylaminobenzene and thionyl chloride are treated with hydrazine hydrate and the products ring closed; in (8), (9), (11) and (12) the acid chlorides <FORM:0816749/IV (c)/3> are treated with hydrazine hydrate and the products ring closed; and in (10) the dyestuff aniline-2-carboxylic acid butyl ester --> 4-methoxy - 3 - acetoacetylaminobenzoic acid is treated with thionyl chloride and the acid chloride thus obtained is treated with hydrazine hydrate and the product ring closed, the final dyestuffs being used to colour polyvinyl chloride in yellow, red and blue tints.